US8206520B2 - Method of forming ductile metallic glasses in ribbon form - Google Patents

Method of forming ductile metallic glasses in ribbon form Download PDF

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US8206520B2
US8206520B2 US12/547,367 US54736709A US8206520B2 US 8206520 B2 US8206520 B2 US 8206520B2 US 54736709 A US54736709 A US 54736709A US 8206520 B2 US8206520 B2 US 8206520B2
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ribbon
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melt
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US20100092329A1 (en
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Daniel James Branagan
Brian E. MEACHAM
Alla V. Sergueeva
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Nanosteel Co Inc
Nano Steel Co Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/02—Amorphous alloys with iron as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15308—Amorphous metallic alloys, e.g. glassy metals based on Fe/Ni
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15333—Amorphous metallic alloys, e.g. glassy metals containing nanocrystallites, e.g. obtained by annealing

Definitions

  • the present disclosure relates to chemistries of matter which may result in amorphous or amorphous/nanocrystalline structures which may yield relatively high strength and relatively high plastic elongation.
  • Metallic nanocrystalline materials and metallic glasses may be considered classes of materials known to exhibit relatively high hardness and strength characteristics. Due to their perceived potential, they may be considered candidates for structural applications. However, these classes of materials may also exhibit relatively limited fracture toughness associated with the relatively rapid propagation of shear bands and/or cracks which may be a concern for the technological utilization of these materials. While these materials may show adequate ductility by testing in compression, when testing in tension these materials may exhibit elongations that may be close to zero and in the brittle regime. The inherent inability of these classes of material to be able to deform in tension at room temperature may be a limiting factor for potential structural applications where intrinsic ductility may be needed to potentially avoid catastrophic failure.
  • Nanocrystalline materials may be understood to include, by definition, polycrystalline structures with a mean grain size below 100 nm. They have been the subject of widespread research since the mid-1980s when Gleiter made the argument that metals and alloys, if made nanocrystalline, may exhibit a number of appealing mechanical characteristics of potential significance for structural applications. But despite relatively attractive properties (high hardness, yield stress and fracture strength), it is well known that nanocrystalline materials may generally show a disappointing and relatively low tensile elongation and may tend to fail in an extremely brittle manner.
  • Valiev, et al. proposed that an increased content of high-angle grain boundaries in nanocrystalline materials could be beneficial to an increase in ductility.
  • relatively ductile base metals have generally been used such as copper, aluminum or zinc with some limited success.
  • Wang, et al. fabricated nanocrystalline Cu with a bimodal grain size distribution (100 nm and 1.7 ⁇ m) based on the thermomechanical treatment of severe plastic deformation. The resulting highly stressed microstructure which was only partially nanoscale was found to exhibit a 65% total elongation to failure while retaining a relative high strength.
  • Lu, et al. produced a nanocrystalline copper coating with nanometer sized twins embedded in submicrometer grained matrix by pulsed electrodeposition.
  • the relatively good ductility and high strength was attributed to the interaction of glide dislocations with twin boundaries.
  • nanocrystalline second-phase particles of 4-10 nm were incorporated into the nanocrystalline Al matrix (about 100 nm).
  • the nanocrystalline particles were found to interact with the slipping dislocation and enhanced the strain hardening rate which leads to the evident improvement of ductility.
  • enhanced tensile ductility has been achieved in a number of nanocrystalline materials such as 15% in pure Cu with mean grain size of 23 nm or 30% in pure Zn with mean grain size of 59 nm.
  • Amorphous metallic alloys i.e. metallic glasses
  • metallic glasses represent a relatively young class of materials, having been first reported in 1960 when Klement, et al., performed rapid-quenched experiments on Au—Si alloys. Since that time, there has been remarkable progress in exploring alloys compositions for glass formers, seeking elemental combinations with ever-lower critical cooling rates for the retention of an amorphous structure. Due to the absence of long-range order, metallic glasses may exhibit what is believed to be somewhat atypical properties, such as relatively high strength, high hardness, large elastic limit, good soft magnetic properties and high corrosion resistance.
  • the present disclosure relates to an iron based alloy composition.
  • the iron based alloy may include iron present in the range of 45 to 70 atomic percent, nickel present in the range of 10 to 30 atomic percent, cobalt present in the range of 0 to 15 atomic percent, boron present in the range of 7 to 25 atomic percent, carbon present in the range of 0 to 6 atomic percent; and silicon present in the range of 0 to 2 atomic percent, wherein the alloy exhibits an elastic strain of greater than 0.5% and a tensile strength of greater than 1 GPa.
  • the present disclosure relates to a method of forming an alloy including melting one or more feedstocks to form an alloy and forming ribbon from the alloy.
  • the alloy may include iron present in the range of 45 to 70 atomic percent, nickel present in the range of 10 to 30 atomic percent, cobalt present in the range of 0 to 15 atomic percent, boron present in the range of 7 to 25 atomic percent, carbon present in the range of 0 to 6 atomic percent; and silicon present in the range of 0 to 2 atomic percent.
  • the ribbon may exhibit an elastic strain of greater than 0.5% and a tensile strength of greater than 1 GPa.
  • FIGS. 1 a through 1 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6 melt-spun at 16 m/s, b) PC7E6JC melt-spun at 16 m/s, c) PC7E6JB melt-spun at 16 m/s, d) PC7E6JA melt-spun at 16 m/s, e) PC7E6J1 melt-spun at 16 m/s, and f) PC7E6J3 melt-spun at 16 m/s.
  • FIGS. 2 a through 2 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6J7 melt-spun at 16 m/s, b) PC7E6J9 melt-spun at 16 m/s, c) PC7E6H1 melt-spun at 16 m/s, d) PC7E6H3 melt-spun at 16 m/s, e) PC7E6H7 melt-spun at 16 m/s, and f) PC7E6H9 melt-spun at 16 m/s.
  • FIGS. 3 a through 3 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6HA melt-spun at 16 m/s, b) PC7E6HB melt-spun at 16 m/s, c) PC7E6HC melt-spun at 16 m/s, d) PC7E6J1H9 melt-spun at 16 m/s, e) PC7E6J3H9 melt-spun at 16 m/s, and f) PC7E6J7H9 melt-spun at 16 m/s.
  • FIGS. 4 a through 4 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6J9H9 melt-spun at 16 m/s, b) PC7E6J1HA melt-spun at 16 m/s, c) PC7E6J3HA melt-spun at 16 m/s, d) PC7E6J7HA melt-spun at 16 m/s, e) PC7E6J9HA melt-spun at 16 m/s, and f) PC7E6J1HB melt-spun at 16 m/s.
  • FIGS. 5 a through 5 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6J3HB melt-spun at 16 m/s, b) PC7E6J7HB melt-spun at 16 m/s, c) PC7E6J1HC melt-spun at 16 m/s, d) PC7E7 melt-spun at 16 m/s.
  • FIGS. 6 a through 6 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6 melt-spun at 10.5 m/s, b) PC7E6JC melt-spun at 10.5 m/s, c) PC7E6JB melt-spun at 10.5 m/s, d) PC7E6JA melt-spun at 10.5 m/s, e) PC7E6J1 melt-spun at 10.5 m/s, and 0 PC7E6J3 melt-spun at 10.5 m/s.
  • FIGS. 7 a through 7 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6J7 melt-spun at 10.5 m/s, b) PC7E6J9 melt-spun at 10.5 m/s, c) PC7E6H1 melt-spun at 10.5 m/s, d) PC7E6H3 melt-spun at 10.5 m/s, e) PC7E6H7 melt-spun at 10.5 m/s, and f) PC7E6H9 melt-spun at 10.5 m/s.
  • FIGS. 8 a through 8 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6HA melt-spun at 10.5 m/s, b) PC7E6HB melt-spun at 10.5 m/s, c) PC7E6HC melt-spun at 10.5 m/s, d) PC7E6J1H9 melt-spun at 10.5 m/s, e) PC7E6J3H9 melt-spun at 10.5 m/s, and f) PC7E6J7H9 melt-spun at 10.5 m/s.
  • FIGS. 9 a through 9 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6J9H9 melt-spun at 10.5 m/s, b) PC7E6J1HA melt-spun at 10.5 m/s, c) PC7E6J3HA melt-spun at 10.5 m/s, d) PC7E6J7HA melt-spun at 10.5 m/s, e) PC7E6J9HA melt-spun at 10.5 m/s, and f) PC7E6J1HB melt-spun at 10.5 m/s.
  • FIGS. 10 a through 10 f illustrate examples of DTA curves of the PC7E6 series alloys showing the presence of glass to crystalline transformation peak(s) and/or melting peak(s); a) PC7E6J3HB melt-spun at 10.5 m/s, b) PC7E6J7HB melt-spun at 10.5 m/s, c) PC7E6J1HC melt-spun at 10.5 m/s, d) PC7E7 melt-spun at 10.5 m/s.
  • FIGS. 11 a and 11 b are images of an example of a two point bend test system; a) image of bend tester, b) close-up schematic of bending process.
  • FIG. 12 illustrates bend test data showing the cumulative failure probability as a function of failure strain for the PC7E6H series alloys melt-spun at 10.5 m/s.
  • FIG. 13 illustrates bend test data showing the cumulative failure probability as a function of failure strain for the PC7E6J series alloys melt-spun at 10.5 m/s.
  • FIG. 14 illustrates the results on the PC7E6 series alloys which have been melt-spun at 16 m/s and then bent 180° until flat.
  • FIG. 15 illustrates the results of the PC7E6 series alloys which have been melt-spun at 10.5 m/s and then bent 180° until flat.
  • FIG. 16 illustrates examples of hand bent samples of PC7E6HA which have been hand bent 180°; a) melt-spun at 10.5 m/s in a 1 ⁇ 3 atm helium environment, b) melt-spun at 10.5 m/s in a 1 atm air environment, c) melt-spun at 16 m/s in a 1 ⁇ 3 atm helium environment, d) melt-spun at 16 m/s in a 1 atm air environment, e) melt-spun at 30 m/s in a 1 ⁇ 3 atm helium environment, and f) melt-spun at 30 m/s in a 1 atm air environment.
  • FIG. 17 illustrates DTA curves of the PC7E6HA alloy showing the presence of glass to crystalline transformation peak(s); a) melt-spun at 10.5 m/s in a 1 ⁇ 3 atm helium environment (also showing melting behavior), b) melt-spun at 10.5 m/s in a 1 atm air environment, c) melt-spun at 16 m/s in a 1 ⁇ 3 atm helium environment, d) melt-spun at 16 m/s in a 1 atm air environment, e) melt-spun at 30 m/s in a 1 ⁇ 3 atm helium environment, and f) melt-spun at 30 m/s in a 1 atm air environment.
  • FIG. 18 illustrates X-ray diffraction scans of the PC7E6J1 sample melt-spun at 16 m/s; wherein the top curve illustrates the free side and the bottom curve illustrates the wheel side.
  • FIG. 19 illustrates X-ray diffraction scans of the PC7E6J1 sample melt-spun at 10.5 m/s; wherein the top curve illustrates the free side, and the bottom curve illustrates the wheel side.
  • FIGS. 20 a through 20 c illustrate SEM backscattered electron micrographs of the PC7E6; a) low magnification showing the entire ribbon cross section, note the presence of isolated points of porosity, b) medium magnification of the ribbon structure, c) high magnification of the ribbon structure.
  • FIGS. 21 a through 21 c illustrate SEM backscattered electron micrographs of the PC7e6HA; a) low magnification showing the entire ribbon cross section, b) medium magnification of the ribbon structure, note the presence of isolated points of crystallinity, c) high magnification of the ribbon structure.
  • FIG. 22 illustrates a stress strain curve for the PC7E6HA alloy melt-spun at 16 m/s.
  • FIG. 23 illustrates a SEM secondary electron image of the PC7E6HA alloy melt-spun at 16 m/s and then tensile tested.
  • FIG. 24 illustrates a stress strain curve for the PC7E7 alloy melt-spun at 16 m/s.
  • FIG. 25 illustrates a SEM secondary electron image of the PC7E7 alloy melt-spun at 16 m/s and then tensile tested. Note the presence of the crack on the right hand side of the picture (black) and the presence of multiple shear bands indicating a large plastic zone in front of the crack tip.
  • the present disclosure relates to an iron based alloy, wherein the iron based glass forming alloy may include, consist essentially of, or consist of about 45 to 70 atomic percent (at %) Fe, 10 to 30 at % Ni, 0 to 15 at % Co, 7 to 25 at % B, 0 to 6 at % C, and 0 to 2 at % Si.
  • the level of iron may be 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, and 70 atomic percent.
  • the level of nickel may be 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 and 30 atomic percent.
  • the level of cobalt may be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, and 15 atomic percent.
  • the level of boron may be 7, 8, 9, 10, 11, 12, 13 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 and 25 atomic percent.
  • the level of carbon may be 0, 1, 2, 3, 4, 5 and 6 atomic percent.
  • the level of silicon may be 0, 1 and 2 atomic percent.
  • the glass forming chemistries may exhibit critical cooling rates for metallic glass formation of less than 100,000 K/s, including all values and increments in the range of 10 3 K/s to 10 5 K/s.
  • Critical cooling rate may be understood as a cooling rate that provides for formation of glassy fractions within the alloy composition.
  • the iron based glass forming alloy may result in a structure that may consist primarily of metallic glass. That is at least 50% or more of the metallic structure, including all values and increments in the range of 50% to 99%, in 1.0% increments, may be glassy. Accordingly, it may be appreciated that little ordering on the near atomic scale may be present, i.e., any ordering that may occur may be less than 50 nm.
  • the iron based alloy may exhibit a structure that includes, consists essentially of, or consists of metallic glass and crystalline phases wherein the crystalline phases may be less than 500 nm in size, including all values and increments between 1 nm and 500 nm in 1 nm increments.
  • the alloys may include, consist essentially of, or consist of iron present in the range of 46 at % to 69 at %; nickel present in the range of 12 at % to 27 at %; optionally cobalt, which if present, may be present in the range of 2 at % to 15 at %; boron present in the range of 12 at % to 16 at %; optionally carbon, which if present, may be present in the range of 4 at % to 5 at %; optionally silicon, which if present, may be present in the range of 0.4 at % to 0.5 at %.
  • the alloys may include the above alloying elements at 100 at % and impurities may be present in a range of 0.1 at % to 5.0 at %, including all values and increments therein. Impurities may be introduced by, among other mechanisms, feedstock compositions, processing equipment, reactivity with the environment during processing, etc.
  • the alloys may be produced by melting one or more feedstock compositions, which may include individual elements or elemental combinations.
  • the feedstocks may be provided as powders or in other forms as well.
  • the feedstocks may be melted by radio frequency (rf) induction, electric arc furnaces, plasma arc furnaces, or other furnaces or apparatus using a shielding gas, such as an argon or helium gas.
  • rf radio frequency
  • the feedstocks Once the feedstocks have been melted, they may be formed into ingots shielded in an inert gas environment.
  • the ingots may be flipped and remelted to increase and/or improve homogeneity.
  • the alloys may then be meltspun into ribbon having widths up to about 1.25 mm.
  • Melt spinning may be performed at, for example, tangential velocities in the range of 5 to 25 meter per second, including all values and increments therein.
  • the ribbon may have a thickness in the range of 0.02 mm to 0.15 mm, including all values and increments therein.
  • Other processes may be used as well, such as twin roll casting or other relatively rapid cooling processes capable of cooling the alloys at a rate of 100,000 K/s or less.
  • the above alloys may exhibit a density in the range of 7.70 grams per cubic centimeter to 7.89 grams per cubic centimeter, +/ ⁇ 0.01 grams per cubic centimeter, including all values and increments therein.
  • the alloys may exhibit one or more glass to crystalline transition temperatures in the range of 410° C. to 500° C., including all values and increments therein, measured using DSC (Differential Scanning Calorimetry) at a rate of 10° C. per minute.
  • Glass to crystalline transition temperature may be understood as a temperature in which crystal structures begin formation and growth out of the glassy alloy.
  • the primary onset glass to crystalline transition temperature may be in the range of 415° C. to 474° C.
  • the secondary onset glass to crystalline transition temperature may be in the range of 450° C. to 488° C., including all values and increments therein, again measured by DSC at a rate of 10° C. per minute.
  • the primary peak glass to crystalline transition temperature may be in the range of 425° C. to 479° C. and the secondary peak glass to crystalline transition temperature may be in the range of 454° C. to 494° C., including all values and increment therein, again measured by DSC at a rate of 10° C. per minute.
  • the enthalpy of transformation may be in the range of ⁇ 40.6 J/g to ⁇ 210 J/g, including all values and increments therein.
  • DSC may be performed under an inert gas to prevent oxidation of the samples, such as high purity argon gas.
  • the above alloys may exhibit initial melting temperatures in the range of 1060° C. to 1120° C.
  • Melting temperature may be understood as the temperature at which the state of the alloy changes from solid to liquid.
  • the alloys may exhibit a primary onset melting temperature in the range of 1062° C. to 1093° C. and a secondary onset melting temperature in the range of 1073° C. to 1105° C., including all values and increments therein, as measured by DSC at a rate of 10° C. per minute.
  • the primary peak melting temperature may be in the range of 1072° C. to 1105° C. and the secondary peak melting temperature may be in the range of 1081° C. to 1113° C., including all values and increments therein, measured by DSC at a rate of 10° C. per minute.
  • DSC may be performed under an inert gas to prevent oxidation of the samples, such as high purity argon gas.
  • the iron based glass forming alloys may result in a structure that exhibits a Young's Modulus in the range of 119 to 134 GPa, including all values and increments therein.
  • Young's Modulus may be understood as the ratio of unit stress to unit strain within the proportional limit of a material in tension or compression.
  • the alloys may also exhibit an ultimate or failure strength in the range of greater than 1 GPa, such as in the range of 1 GPa to 5 GPa, such as 2.7 GPa to 4.20 GPa, including all values and increments therein. Failure strength may be understood as the maximum stress value.
  • the alloys may exhibit an elastic strain 0.5% or greater, including all values and increments in the range of 0.5 to 4.0%.
  • Elastic strain may be understood as the change in a dimension of a body under a load divided by the initial dimension in the elastic region.
  • the alloy may also exhibit a tensile or bending strain greater than 2% and up to 97%, including all values and increments therein.
  • the tensile or bending strain may be understood as the maximum change in a dimension of a body under a load divided by the initial dimension.
  • the alloy may also exhibit a combination of the above properties, such as a failure strength greater than 1 GPa and a tensile or bending strain greater than 2%.
  • the resulting alloys may also exhibit amorphous fractions, nanocrystalline structures and/or microcrystalline structures.
  • microcrystalline may be understood to include structures that exhibit a mean grain size of 500 nm or less, including all values and increments in the range of 100 nm to 500 nm.
  • Nanocrystalline may be understood to include structures that exhibit a mean grain size of below 100 nm, such as in the range of 50 nm to 100 nm, including all values and increments therein.
  • Amorphous may be understood as including structures that exhibit relatively little to no order, exhibiting a mean grain size, if grains are present, in the range of less than 50 nm.
  • the ingots were melted in a 1 ⁇ 3 atm helium atmosphere using RF induction and then ejected onto a 245 mm diameter copper wheel which was traveling at tangential velocities which varied from 5 to 25 m/s.
  • the resulting PC7E6 series ribbon that was produced had widths which were typically up to ⁇ 1.25 mm and thickness from 0.02 to 0.15 mm.
  • the density of the alloys in ingot form was measured using the Archimedes method in a specially constructed balance allowing weighing in both air and distilled water.
  • the density of the arc-melted 15 gram ingots for each alloy is tabulated in Table 2 and was found to vary from 7.70 g/cm 3 to 7.89 g/cm 3 .
  • Experimental results have revealed that the accuracy of this technique is + ⁇ 0.01 g/cm 3 .
  • the two-point bending method for strength measurement was developed for thin, highly flexible specimens, such as optical fibers and ribbons.
  • the method involves bending a length of tape (fiber, ribbon, etc.) into a “U” shape and inserting it between two flat and parallel faceplates.
  • One faceplate is stationary while the second is moved by a computer controlled stepper motor so that the gap between the faceplates can be controlled to a precision of better than ⁇ 5 ⁇ m with an ⁇ 10 ⁇ m systematic uncertainty due to the zero separation position of the faceplates ( FIG. 11 ).
  • the stepper motor moves the faceplates together at a precisely controlled specified speed at any speed up to 10,000 ⁇ m/s. Fracture of the tape is detected using an acoustic sensor which stops the stepper motor. Since for measurements on the tapes, the faceplate separation at failure varied between 2 and 11 mm, the precision of the equipment does not influence the results.
  • ⁇ f 1.198 ⁇ ( d D - d ) ( 1 )
  • ⁇ f 1.198 ⁇ ⁇ E ⁇ ( d D - d ) ( 2 )
  • d is the tape thickness
  • D is the faceplate separation at failure.
  • Young's modulus was measured from nanoindentation testing and was found to vary from 119 to 134 GPa for the PC7E6 series alloys. As indicated earlier, for the samples not measured, Young's Modulus was estimated to be 125 GPa.
  • the shape of the tape between the faceplates is an elastica which is similar to an ellipse with an aspect ratio of ⁇ 2:1. The equation assumes elastic deformation of the tape.
  • Equation #3 The strength data for materials is typically fitted to a Weibull distribution as shown in Equation #3:
  • m is the Weibull modulus (an inverse measure of distribution width) and ⁇ 0 is the Weibull scale parameter (a measure of centrality, actually the 63% failure probability).
  • m is a dimensionless number corresponding to the variability in measured strength and reflects the distribution of flaws. This distribution is widely used because it is simple to incorporate Weibull's weakest link theory which describes how the strength of specimens depends on their size.
  • FIGS. 12 and 13 two point bend results are shown giving the cumulative failure probability as a function of failure strain for the PC7E6H and PC7E6J series alloys, respectively, which have been melt-spun at 10.5 m/s. Note that every data point in these Figures represents a separate bend test and for each sample, 17 to 25 measurements were done. In Table 6, the results on these 10.5 m/s bend test measurements are tabulated including Young's Modulus (GPA and psi), failure strength (GPA and psi), Weibull Modulus, average strain (%), and maximum strain (%). The Young's modulus of 125 GPa was used for bend testing calculations of strength which is an average value for such types of alloys.
  • the Weibull Modulus was found to vary from 2.97 to 8.49 indicating the presence of macrodefects in some of the ribbons causing premature failure.
  • the average strain in percent was calculated based on the sample set that broke during two-point bend testing. The average strain ranged from 1.52 to 2.15%.
  • the maximum strain in percent during bending was found to vary from 2.3% to 3.36%. Failure strength values were calculated from 2.87 to 4.20 GPa.
  • the strain may be in the range of ⁇ 57% to ⁇ 97% strain in the tension side of the ribbon.
  • the results show a varied behavior including brittle, bendable on one side along entire length (not counting occasion localized areas containing defects), bendable in isolated spots only in one direction, and bendable on both sides (i.e. wheel and free sides).
  • FIG. 14 there is a wide composition regime with respect to nickel and cobalt, where the samples can be bent in both directions.
  • the thick ribbons i.e. those processed at 10.5 m/s
  • no samples were found to be bendable in both directions.
  • FIG. 15 there is a fairly narrow composition regime (i.e.
  • nickel and cobalt ratios where the ribbons are bendable flat along the entire length in one direction.
  • These Figures illustrate the effects of changing nickel and cobalt content on bending response and intrinsic elongation. Note however that by changing the base elements including boron, carbon, silicon, and iron, it is expected that the bending response can be changed and enhanced especially at the lower wheel speeds such as 10.5 m/s.
  • the as-spun ribbons were then cut and four to six pieces of ribbon were placed on an off-cut SiO 2 single crystal (zero-background holder).
  • the ribbons were situated such that either the shiny side (free side) or the dull side (wheel side) were positioned facing up on the holder.
  • a small amount of silicon powder was placed on the holder as well, and then pressed down with a glass slide so that the height of the silicon matched the height of the ribbon, which will allow for matching any peak position errors in subsequent detailed phase analysis.
  • X-ray diffraction scans were taken from 20 to 100 degrees (two theta) with a step size of 0.02 degrees and at a scanning rate of 2 degrees/minute.
  • the X-ray tube settings with a copper target were 40 kV and 44 mA.
  • X-ray diffraction scans are shown for the PC7E6J1 alloy melt-spun at 16 m/s showing the free side and wheel sides.
  • X-ray diffraction scans are shown for the PC7E6J1 alloy melt-spun at 10.5 m/s showing the free side and wheel sides.
  • SEM scanning electron microscopy
  • FIG. 21 SEM backscattered electron micrographs are shown of the PC7E6HA alloy at three different magnifications. As shown, the images show generally a featureless microstructure but in the region at medium magnification, (i.e. FIG. 21 b ), isolated points of crystallinity are found on a scale of approximately 500 nm. This may indicate that a key component in getting high elongation may be crystalline precipitates in a glass matrix.
  • the Young's Modulus was found to be 112.8 GPA with a measured tensile strength of 3.17 GPa and a total elongation of 2.9%. Note that the initial tensile testing was performed with a relatively large gauge length (23 mm) which is approximately a factor of 10 longer than what it should be based on the sample cross sectional area. Additionally, the grips were not perfectly aligned in both the horizontal and vertical directions. Thus during tensile testing, misalignment and torsional strains were occurring which limited the maximum elongation and tensile strength. In FIG. 23 , a SEM backscattered electron micrograph is shown of the PC7E6HA alloy melt-spun at 16 m/s after tensile testing.
  • the localized strain is estimated to be ⁇ 30% in the axial direction and ⁇ 98% in the longitudinal direction.
  • the Young's Modulus was found to be 108.6 GPA with a measured tensile strength of 2.70 GPa and a total elongation of 4.2%. Note that the initial tensile testing was done with an excessively large gauge length (23 mm) which is approximately a factor of 10 longer than what it should based on the sample cross sectional area. Additionally, the grips were not perfectly aligned in both the horizontal and vertical directions. Thus during tensile testing, misalignment and torsional strains were occurring which limited the maximum elongation and tensile strength. In FIG. 25 , a SEM backscattered electron micrograph is shown of the PC7E7 alloy melt-spun at 16 m/s after tensile testing.

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US20110108166A1 (en) * 2009-11-06 2011-05-12 The Nanosteel Company, Inc. Utilization of Amorphous Steel Sheets In Honeycomb Structures
US8497027B2 (en) * 2009-11-06 2013-07-30 The Nanosteel Company, Inc. Utilization of amorphous steel sheets in honeycomb structures

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